On-chip electrocatalytic microdevices.

On-chip electrocatalytic microdevices (OCEMs) are an emerging electrochemical platform specialized for investigating nanocatalysts at the microscopic level. The OCEM platform allows high-precision electrochemical measurements at the individual nanomaterial level and, more importantly, offers unique perspectives inaccessible with conventional electrochemical methods. This protocol describes the critical concepts, experimental standardization, operational principles and data analysis of OCEMs. Specifically, standard protocols for the measurement of the electrocatalytic hydrogen evolution reaction of individual 2D nanosheets are introduced with data validation, interpretation and benchmarking. A series of factors (e.g., the exposed area of material, the choice of passivation layer and current leakage) that could have effects on the accuracy and reliability of measurement are discussed. In addition, as an example of the high adaptability of OCEMs, the protocol for in situ electrical transport measurement is detailed. We believe that this protocol will promote the general adoption of the OCEM platform and inspire further development in the near future. This protocol requires essential knowledge in chemical synthesis, device fabrication and electrochemistry.

Surfactant-Free Ultrasonication-Assisted Synthesis of 2d Tellurium Based on Metastable 1T'-MoTe2.

Elemental 2D materials (E2DMs) have been attracting considerable attention owing to their chemical simplicity and excellent/exotic properties. However, the lack of robust chemical synthetic methods seriously limits their potential. Here, a surfactant-free liquid-phase synthesis of high-quality 2D tellurium is reported based on ultrasonication-assisted exfoliation of metastable 1T'-MoTe2 . The as-grown 2D tellurium nanosheets exhibit excellent single crystallinity, ideal 2D morphology, surfactant-free surface, and negligible 1D by-products. Furthermore, a unique growth mechanism based on the atomic escape of Te atoms from metastable transition metal dichalcogenides and guided 2D growth in the liquid phase is proposed and verified. 2D tellurium-based field-effect transistors show ultrahigh hole mobility exceeding 1000 cm2  V-1  s-1 at room temperature attributing to the high crystallinity and surfactant-free surface, and exceptional chemical and operational stability using both solid-state dielectric and liquid-state electrical double layer. The facile ultrasonication-assisted synthesis of high-quality 2D tellurium paves the way for further exploration of E2DMs and expands the scope of liquid-phase exfoliation (LPE) methodology toward the controlled wet-chemical synthesis of functional nanomaterials.

Filling the Gap between Heteroatom Doping and Edge Enrichment of 2D Electrocatalysts for Enhanced Hydrogen Evolution.

Composition modulation and edge enrichment are established protocols to steer the electronic structures and catalytic activities of two-dimensional (2D) materials. It is believed that a heteroatom enhances the catalytic performance by activating the chemically inert basal plane of 2D crystals. However, the edge and basal plane have inherently different electronic states, and how the dopants affect the edge activity remains ambiguous. Here we provide mechanistic insights into this issue by monitoring the hydrogen evolution reaction (HER) performance of phosphorus-doped MoS2 (P-MoS2) nanosheets via on-chip electrocatalytic microdevices. Upon phosphorus doping, MoS2 nanosheet gets catalytically activated and, more importantly, shows higher HER activity in the edge than the basal plane. In situ transport measurement demonstrates that the improved HER performance of P-MoS2 is derived from intrinsic catalytic activity rather than charge transfer. Density functional theory calculations manifest that the edge sites of P-MoS2 are energetically more favorable for HER. The finding guides the rational design of edge-dominant P-MoS2, reaching a minuscule onset potential of ∼30 mV and Tafel slope of 48 mV/dec that are benchmarked against other activation methods. Our results disclose the hitherto overlooked edge activity of 2D materials induced by heteroatom doping that will provide perspectives for preparing next-generation 2D catalysts.

On-Chip Investigation of Electrocatalytic Oxygen Reduction Reaction of 2D Materials.

The on-chip electrocatalytic microdevice (OCEM) is an emerging platform specialized in the electrochemical investigation of single-entity nanomaterials, which is ideal for probing the intrinsic catalytic properties, optimizing performance, and exploring exotic mechanisms. However, the current catalytic applications of OCEMs are almost exclusively in electrocatalytic hydrogen/oxygen evolution reactions with minimized influence from the mass transfer. Here, an OCEM platform specially tailored to investigate the electrocatalytic oxygen reduction reaction (ORR) at a microscopic level by introducing electrolyte convection through a microfluidic flow cell is reported. The setup is established on gold microelectrodes and later successfully applied to investigate how Ar-plasma treatment affects the ORR activities of 2H MoS2 . This study finds that Ar-plasma treatment significantly enhances the ORR performance of MoS2 nanosheets owing to the introduction of surface defects. This study paves the way for highly efficient microscopic investigation of diffusion-controlled electrocatalytic reactions.

Efficient and Stable 3D/2D Perovskite Solar Cells through Vertical Heterostructures with (BA)4 AgBiBr8 Nanosheets.

Perovskite solar cells (PVSCs) have drawn great attention due to their high processability and superior photovoltaic properties. However, their further development is often hindered by severe nonradiative recombination at interfaces that decreases power conversion efficiency (PCE). To this end, a facile strategy to construct a 3D/2D vertical heterostructure to reduce the energy loss in PVSCs is developed. The heterostructure is contrived through the van der Waals integration of 2D perovskite ((BA)4 AgBiBr8 ) nanosheets onto the surface of 3D-FAPbI3 -based perovskites. The large bandgap of (BA)4 AgBiBr8 enables the formation of type-I heterojunction with 3D-FAPbI3 -based perovskites, which serves as a barrier to suppress the trap-assisted recombination at the interface. As a result, a satisfying PCE of 24.48% is achieved with an improved open-circuit voltage (VOC ) from 1.13 to 1.17 V. Moreover, the 2D perovskite nanosheets can effectively mitigate the iodide ion diffusion from perovskite to the metal electrode, hence enhancing the device stability. 3D/2D architectured devices retain ≈90% of their initial PCE under continuous illumination or heating after 1000 h, which are superior to 3D-based devices. This work provides an effective and controllable strategy to construct 3D/2D vertical heterostructure to simultaneously boost the efficiency and stability of PVSCs.

Preparation of 2D Molybdenum Phosphide via Surface-Confined Atomic Substitution.

The emerging nonlayered 2D materials (NL2DMs) are sparking immense interest due to their fascinating physicochemical properties and enhanced performance in many applications. NL2DMs are particularly favored in catalytic applications owing to the extremely large surface area and low-coordinated surface atoms. However, the synthesis of NL2DMs is complex because their crystals are held together by strong isotropic covalent bonds. Here, nonlayered molybdenum phosphide (MoP) with well-defined 2D morphology is synthesized from layered molybdenum dichalcogenides via surface-confined atomic substitution. During the synthesis, the molybdenum dichalcogenide nanosheet functions as the host matrix where each layer of Mo maintains their hexagonal arrangement and forms isotropic covalent bonds with P that substitutes S, resulting in the conversion from layered van der Waals material to a covalently bonded NL2DM. The MoP nanosheets converted from few-layer MoS2 are single crystalline, while those converted from monolayers are amorphous. The converted MoP demonstrates metallic charge transport and desirable performance in the electrocatalytic hydrogen evolution reaction (HER). More importantly, in contrast to MoS2 , which shows edge-dominated HER performance, the edge and basal plane of MoP deliver similar HER performance, which is correlated with theoretical calculations. This work provides a new synthetic strategy for high-quality nonlayered materials with well-defined 2D morphology for future exploration.

Electrospinning metal Phosphide/Carbon nanofibers from Phytic Acid for hydrogen evolution reaction catalysts.

This paper reports a general electrospinning method to prepare various metal phosphide/carbon nanofibers composite for electrochemical hydrogen evolution reaction (HER) catalysts. An earth-abundant organic acid-phytic acid is successfully incorporated into a conventional electrospinning precursor as the phosphorus source, and continuous nanofibers can be obtained through spinning. After heat treatment, metal phosphide/carbon composite nanofibers can be obtained, with fine phosphide nanoparticles well dispersed on the surface of an interconnected carbon backbone network. Such fibrous structures offer fast charge transfer pathways and enlarged active surface area, which are beneficial for electrocatalysts. As a result, enhance HER catalytic activity can be achieved.

Rational Design of Porous Structured Nickel Manganese Sulfides Hexagonal Sheets-in-Cage Structures as an Advanced Electrode Material for High-Performance Electrochemical Capacitors.

The design of hierarchical electrodes comprising multiple components with a high electrical conductivity and a large specific surface area has been recognized as a feasible strategy to remarkably boost pseudocapacitors. Herein, we delineate hexagonal sheets-in-cage shaped nickel-manganese sulfides (Ni-Mn-S) with nanosized open spaces for supercapacitor applications to realize faster redox reactions and a lower charge-transfer resistance with a markedly enhanced specific capacitance. The hybrid was facilely prepared through a two-step hydrothermal method. Benefiting from the synergistic effect between Ni and Mn active sites with the improvement of both ionic and electric conductivity, the resulting Ni-Mn-S hybrid displays a high specific capacitance of 1664 F g-1 at a current density of 1 A g-1 and a capacitance of 785 F g-1 is maintained at a current density of 50 A g-1 , revealing an outstanding capacity and rate performance. The asymmetric supercapacitor device assembled with the Ni-Mn-S hexagonal sheets-in-cage as the positive electrode delivers a maximum energy density of 40.4 Wh kg-1 at a power density of 750 W kg-1 . Impressively, the cycling retention of the as-fabricated device after 10 000 cycles at a current density of 10 A g-1 reaches 85.5 %. Thus, this hybrid with superior capacitive performance holds great potential as an effective charge-storage material.

Synthesis of coaxial carbon@NiMoO4 composite nanofibers for supercapacitor electrodes.

This work reports the synthesis of coaxial carbon@NiMoO4 nanofibers for supercapacitor electrode applications. Thin NiMoO4 nanosheets are uniformly coated on the conductive electrospun carbon nanofibers by a microwave assisted hydrothermal method to form a hierarchical structure, which increases the porosity as well as the conductivity of the electrode. The thickness of the NiMoO4 can be easily adjusted by varying the precursor concentrations. The high specific surface area (over 280 m2 g-1) and conductive carbon nanofiber backbone increase the utilization of the active pseudocapacitive NiMoO4 phase, resulting a high specific capacitance of 1840 F g-1.

Co9S8 nanoparticle-decorated carbon nanofibers as high-performance supercapacitor electrodes.

This work reported Co9S8 nanoparticle-decorated carbon nanofibers (CNF) as a supercapacitor electrode. By using a mild ion-exchange method, the cobalt oxide-based precursor nanoparticles were transformed to Co9S8 nanoparticles in a microwave hydrothermal process, and these nanoparticles were decorated onto a carbon nanofiber backbone. The composition of the nanofibers can be readily tuned by varying the Co acetate content in the precursor. The porous carbon nanofibers offered a fast electron transfer pathway while the well dispersed Co9S8 nanoparticles acted as the redox center for energy storage. As a result, high specific capacitance of 718 F g-1 at 1 A g-1 can be achieved with optimized Co9S8 loading. The assembled asymmetric supercapacitor with Co9S8/CNF as the cathode showed a high energy density of 23.8 W h kg-1 at a power density of 0.75 kW kg-1 and good cycling stability (16.9% loss over 10 000 cycles).