Activating a Two-Dimensional PtSe2 Basal Plane for the Hydrogen Evolution Reaction through the Simultaneous Generation of Atomic Vacancies and Pt Clusters.

Two-dimensional (2D) PtSe2 has emerged as a promising ultrathin electrocatalyst due to its excellent catalytic activity and conductivity. However, the PtSe2 basal plane is inert for the hydrogen evolution reaction (HER), which greatly limits its electrocatalytic performance. Here, in light of theoretical calculations, we designed a facile approach for activating the 2D PtSe2 basal plane for the HER by simultaneously introducing atomic vacancies of Se, Pt, and Pt clusters through a mild Ar plasma treatment. We tracked changes in the structures and catalytic performance of PtSe2 by combining microscopic imaging, spectroscopic mapping, and electrochemical measurements in microcells. The highest performance of the activated PtSe2 basal plane that we obtained was superior to those of other 2D transition metal dichalcogenide-based electrocatalysts measured in microcells in terms of the overpotential, the Tafel slope, and the exchange current density. This study demonstrates the great potential of activated 2D PtSe2 as an ultrathin catalyst for the HER and provides new insights on the rational design of 2D electrocatalysts.

1D/2D Heterostructures as Ultrathin Catalysts for Hydrogen Evolution Reaction.

2D MoS2 has emerged as a promising alternative to Pt-based catalysts for hydrogen evolution reaction (HER) due to its low cost and earth abundance. However, insufficient active sites of basal plane and poor conductivity become the foremost factors restricting the catalytic performance of MoS2 . Here, a facile strategy is presented to enhance the HER performance of MoS2 by converting its 2D structure into 1D/2D heterostructures of Mo6 Te6 /MoS2(1- x ) Te2 x by the in situ tellurization. As-prepared 1D/2D heterostructures exhibit excellent HER performance with the Tafel slope of ≈56 mV dec-1 (only one-third of that for pristine MoS2 ). The enhanced HER catalytic activity is attributed to more Te/S vacancies introduced by tellurization, which serve as the active sites as suggested by theoretical calculations. Besides, the formation of highly conductive well-aligned quasi-1D Mo6 Te6 nanobelts facilitate charge transport in HER. Previous work provides a facile approach to construct mixed dimensional materials, and opens up a new avenue to the properties modulation of 2D transition metal chalcogenides.

Unveiling the Layer-Dependent Catalytic Activity of PtSe2 Atomic Crystals for the Hydrogen Evolution Reaction.

Two-dimensional (2D) PtSe2 shows the most prominent layer-dependent electrical properties among various 2D materials and high catalytic activity for hydrogen evolution reaction (HER), and therefore, it is an ideal material for exploring the structure-activity correlations in 2D systems. Here, starting with the synthesis of single-crystalline 2D PtSe2 with a controlled number of layers and probing the HER catalytic activity of individual flakes in micro electrochemical cells, we investigated the layer-dependent HER catalytic activity of 2D PtSe2 from both theoretical and experimental perspectives. We clearly demonstrated how the number of layers affects the number of active sites, the electronic structures, and electrical properties of 2D PtSe2 flakes and thus alters their catalytic performance for HER. Our results also highlight the importance of efficient electron transfer in achieving optimum activity for ultrathin electrocatalysts. Our studies greatly enrich our understanding of the structure-activity correlations for 2D catalysts and provide new insight for the design and synthesis of ultrathin catalysts with high activity.

Electrochemical Construction of Edge-Contacted Metal-Semiconductor Junctions with Low Contact Barrier.

2D semiconductors, such as MoS2 have emerged as promising ultrathin channel materials for the further scaling of field-effect transistors (FETs). However, the contact barrier at the metal-2D semiconductor junctions still significantly limits the device's performance. By extending the application of electrochemical deposition in 2D electronics, a distinct approach is developed for constructing metal-2D semiconductor junctions in an edge-contacted configuration through the edge-guided electrodeposition of varied metals. Both high-resolution microscopic imaging and electrical transport measurements confirm the successful creation of high-quality Pd-2D MoS2 junctions in desired geometry by combining electrodeposition with lithographic patterning. FETs are fabricated on the obtained Pd-2D MoS2 junctions and it is confirmed that these junctions exhibit a reduced contact barrier of ≈20 meV and extremely low contact resistance of 290 Ω µm and thus increase the averaged mobility of MoS2 FETs to ≈108 cm2 V -1 s-1 . This approach paves a new way for the construction of metal-semiconductor junctions and also demonstrates the great potential of the electrochemical deposition technique in 2D electronics.

Chemical Synthesis and Integration of Highly Conductive PdTe2 with Low-Dimensional Semiconductors for p-Type Transistors with Low Contact Barriers.

Low-dimensional semiconductors provide promising ultrathin channels for constructing more-than-Moore devices. However, the prominent contact barriers at the semiconductor-metal electrodes interfaces greatly limit the performance of the obtained devices. Here, a chemical approach is developed for the construction of p-type field-effect transistors (FETs) with low contact barriers by achieving the simultaneous synthesis and integration of 2D PdTe2 with various low-dimensional semiconductors. The 2D PdTe2 synthesized through a quasi-liquid process exhibits high electrical conductivity (≈4.3 × 106 S m-1 ) and thermal conductivity (≈130 W m-1 K-1 ), superior to other transition metal dichalcogenides (TMDCs) and even higher than some metals. In addition, PdTe2 electrodes with desired geometry can be synthesized directly on 2D MoTe2 and other semiconductors to form high-performance p-type FETs without any further treatment. The chemically derived atomically ordered PdTe2 -MoTe2 interface results in significantly reduced contact barrier (65 vs 240 meV) and thus increases the performance of the obtained devices. This work demonstrates the great potential of 2D PdTe2 as contact materials and also opens up a new avenue for the future device fabrication through the chemical construction and integration of 2D components.