Electrochemical Generation of Te Vacancy Pairs in PtTe for Efficient Hydrogen Evolution.

Two-dimensional (2D) van der Waals materials are increasingly seen as potential catalysts due to their unique structures and unmatched properties. However, achieving precise synthesis of these remarkable materials and regulating their atomic and electronic structures at the most fundamental level to enhance their catalytic performance remain a significant challenge. In this study, we synthesized single-crystal bulk PtTe crystals via chemical vapor transport and subsequently produced atomically thin, large PtTe nanosheets (NSs) through electrochemical cathode intercalation. These NSs are characterized by a significant presence of Te vacancy pairs, leading to undercoordinated Pt atoms on their basal planes. Experimental and theoretical studies together reveal that Te vacancy pairs effectively optimize and enhance the electronic properties (such as charge distribution, density of states near the Fermi level, and d-band center) of the resultant undercoordinated Pt atoms. This optimization results in a significantly higher percentage of dangling O-H water, a decreased energy barrier for water dissociation, and an increased binding affinity of these Pt atoms to active hydrogen intermediates. Consequently, PtTe NSs featuring exposed and undercoordinated Pt atoms demonstrate outstanding electrocatalytic activity in hydrogen evolution reactions, significantly surpassing the performance of standard commercial Pt/C catalysts.

Advances in heterogeneous single-cluster catalysis.

Heterogeneous single-cluster catalysts (SCCs) comprising atomically precise and isolated metal clusters stabilized on appropriately chosen supports offer exciting prospects for enabling novel chemical reactions owing to their broad structural diversity with unparalled opportunities for engineering their properties. Although the pioneering work revealed intriguing performance trends of size-selected metal clusters deposited on supports, synthetic and analytical challenges hindered a thorough understanding of surface chemistry under realistic conditions. This Review underscores the importance of considering the cluster environment in SCCs, encompassing the development of robust metal-support interactions, precise control over the ligand sphere, the influence of reaction media and dynamic behaviour, to uncover new reactivities. Through examples, we illustrate the criticality of tailoring the entire catalytic ensemble in SCCs to achieve stable and selective performance with practically relevant metal coverages. This expansion in application scope transcends from model reactions to complex and technically relevant reactions. Furthermore, we provide a perspective on the opportunities and future directions for SCC design within this rapidly evolving field.

Triggering Pt Active Sites in Basal Plane of Van der Waals PtTe2 Materials by Amorphization Engineering for Hydrogen Evolution.

Exposing active sites and optimizing their binding strength to reaction intermediates are two essential strategies to significantly improve the catalytic performance of 2D materials. However, pursuing an efficient way to achieve these goals simultaneously remains a considerable challenge. Here, using 2D PtTe2 van der Waals material with a well-defined crystal structure and atomically thin thickness as a model catalyst, it is observed that a moderate calcination strategy can promote the structural transformation of 2D crystal PtTe2 nanosheets (c-PtTe2 NSs) into oxygen-doped 2D amorphous PtTe2 NSs (a-PtTe2 NSs). The experimental and theoretical investigations cooperatively reveal that oxygen dopants can break the inherent Pt-Te covalent bond in c-PtTe2 NSs, thereby triggering the reconfiguration of interlayer Pt atoms and exposing them thoroughly. Meanwhile, the structural transformation can effectively tailor the electronic properties (e.g., the density of state near the Fermi level, d-band center, and conductivity) of Pt active sites via the hybridization of Pt 5d orbitals and O 2p orbitals. As a result, a-PtTe2 NSs with large amounts of exposed Pt active sites and optimized binding strength to hydrogen intermediates exhibit excellent activity and stability in hydrogen evolution reaction.

Metal-Catalyst-Controlled Divergent Synthesis of γ-Butyrolactones via Intramolecular Coupling of Epoxides with Alcohols.

A metal-controlled divergent protocol for the synthesis of α- and ß-substituted γ-butyrolactones was developed through intramolecular coupling of epoxides with alcohols. This method provides an efficient and practicable way to afford γ-butyrolactones with good efficiency, excellent regioselectivity, and broad substrate scope.

Ordered clustering of single atomic Te vacancies in atomically thin PtTe2 promotes hydrogen evolution catalysis.

Exposing and stabilizing undercoordinated platinum (Pt) sites and therefore optimizing their adsorption to reactive intermediates offers a desirable strategy to develop highly efficient Pt-based electrocatalysts. However, preparation of atomically controllable Pt-based model catalysts to understand the correlation between electronic structure, adsorption energy, and catalytic properties of atomic Pt sites is still challenging. Herein we report the atomically thin two-dimensional PtTe2 nanosheets with well-dispersed single atomic Te vacancies (Te-SAVs) and atomically well-defined undercoordinated Pt sites as a model electrocatalyst. A controlled thermal treatment drives the migration of the Te-SAVs to form thermodynamically stabilized, ordered Te-SAV clusters, which decreases both the density of states of undercoordinated Pt sites around the Fermi level and the interacting orbital volume of Pt sites. As a result, the binding strength of atomically defined Pt active sites to H intermediates is effectively reduced, which renders PtTe2 nanosheets highly active and stable in hydrogen evolution reaction.

NiPS3 nanoflakes: a nonlinear optical material for ultrafast photonics.

Ultrafast photonics based on two-dimensional (2D) materials has been used to investigate light-matter interactions and laser generation, as well as light propagation, modulation, and detection. Here, 2D metal-phosphorus trichalcogenides, which are known for applications in catalysis and electrochemical storage, also exhibit advantageous photonic properties as nanoflakes that are only a few layers thick. By using an open-aperture Z-scan system, few-layer NiPS3 nanoflakes exhibited a large modulation depth of 56% and a low saturable intensity of 16 GW cm-2 at 800 nm. When NiPS3 nanoflakes were used as a saturable absorber at 1066 nm, highly stable mode-locked pulses were generated. Thus, these results revealed the nonlinear optical properties of NiPS3 nanoflakes which have potential photonics applications, such as modulators, switches, and thresholding devices.

High-Yield Electrochemical Production of Large-Sized and Thinly Layered NiPS3 Flakes for Overall Water Splitting.

Achieving large-sized and thinly layered 2D metal phosphorus trichalcogenides with high quality and yield has been an urgent quest due to extraordinary physical/chemical characteristics for multiple applications. Nevertheless, current preparation methodologies suffer from uncontrolled thicknesses, uneven morphologies and area distributions, long processing times, and inferior quality. Here, a sonication-free and fast (in minutes) electrochemical cathodic exfoliation approach is reported that can prepare large-sized (typically ≈150 µm2 ) and thinly layered (≈70% monolayer) NiPS3 flakes with high crystallinity and pure phase structure with a yield ≈80%. During the electrochemical exfoliation process, the tetra-n-butylammonium salt with a large ionic diameter is decomposed into gaseous species after the intercalation and efficiently expands the tightly stratified bulk NiPS3 crystals, as revealed by in situ and ex situ characterizations. Atomically thin NiPS3 flakes can be obtained by slight manual shaking rather than sonication, which largely preserves in-plane structural integrity with large size and minimum damage. The obtained high quality NiPS3 offers a new and ideal model for overall water splitting due to its inherent fully exposed S and P atoms that are often the active sites for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Consequently, the bifunctional NiPS3 exhibits outstanding performance for overall water splitting.

Co@Co3O4 core-shell particle encapsulated N-doped mesoporous carbon cage hybrids as active and durable oxygen-evolving catalysts.

Cobalt-based nanomaterials are promising candidates as efficient, affordable, and sustainable alternative electrocatalysts for the oxygen evolution reaction (OER). However, the catalytic efficiency of traditional nanomaterials is still far below what is expected, because of their low stability in basic solutions and poor active site exposure yield. Here a unique hybrid nanomaterial comprising Co@Co3O4 core-shell nanoparticle (NP) encapsulated N-doped mesoporous carbon cages on reduced graphene oxide (denoted as Co@Co3O4@NMCC/rGO) is successfully synthesized via a carbonization and subsequent oxidation strategy of a graphene oxide (GO)-based metal-organic framework (MOF). Impressively, the special carbon cage structure is very important for not only leading to a large active surface area, enhanced mass/charge transport capability, and easy release of gas bubbles, but also preventing Co@Co3O4 NPs from aggregation and peeling off during prolonged electrochemical reactions. As a result, in alkaline media, the resulting hybrid materials catalyze the OER with a low onset potential of ∼1.50 V (vs. RHE) and an over-potential of only 340 mV to achieve a stable current density of 10 mA cm(-2) for at least 25 h. In addition, metallic Co cores in Co@Co3O4 provide an alternative way for electron transport and accelerate the OER rate.

[Morphological characteristics of the mandibular first premolars in people from Pearl River Delta region in Guangdong province].

OBJECTIVE: To investigate the morphological characteristics of the mandibular first premolars in people from Pearl River Delta region in Guangdong province using three techniques, including periapical radiographs, the radiographs with files inserted the canals and the clearing technique. METHODS: A total of 363 extracted mandibular first premolars were collected and numbered. Two preoperative radiographs were taken in buccolingual and mesiodistal directions respectively. After access opening, the files were placed in the canals and two other radiographs were taken. The mandibular first premolars with multi-canal system were selected and observed under dental operating microscope (DOM). The mandibular first premolars were made transparent and were categorized using the Vertucci's classification. RESULTS: There were different results among the three approaches. Periapical radiographs could be used to distinguish only between one and multiple canals systems. The incidence of multiple canals was 33.33% from the radiographs with file. The mandibular first premolars had a high frequency (34.44%) of multi-canal system by clearing method. The root canal morphology of the mandibular first premolars showed great variance. The canal orifices of the mandibular first premolars with one or two canal distributed in a buccolingual line. The floor of pulp chamber of the mandibular first premolars with three or four canals was a plat form. CONCLUSION: The mandibular first premolars have a high frequency multi-canal system and could be classified in many categories. Using DOM and radiographs with file is a useful way in judging the canal numbers and categories.