Constructing N-Containing Poly(p-Phenylene) (PPP) Films Through A Cathodic-Dehalogenation Polymerization Method.

Developing the films of N-containing unsubstituted poly(p-phenylene) (PPP) films for diverse applications is significant and highly desirable because the replacement of sp2 C atoms with sp2 N atoms will bring novel properties to the as-prepared polymers. In this research, an electrochemical-dehalogenation polymerization strategy is employed to construct two N-containing PPP films under constant potentials, where 2,5-diiodopyridine (DIPy) and 2,5-dibromopyrazine (DBPz) are used as starting agents. The corresponding polymers are named CityU-23 (for polypyridine) and CityU-24 (for polypyrazine). Moreover, it is found that both polymers can form films in situ on different conductive substrates (i.e., silicon, gold, ITO, and nickel), satisfying potential device fabrication. Furthermore, the as-obtained thin films of CityU-23 and CityU-24 exhibit good performance of alkaline hydrogen evolution reaction with the overpotential of 212.8 and 180.7 mV and the Tafel slope of 157.0 and 122.4 mV dec-1, respectively.

Wet-Chemical Synthesis of Elemental 2D Materials.

Wet-chemical synthesis refers to the bottom-up chemical synthesis in solution, which is among the most popular synthetic approaches towards functional two-dimensional (2D) materials. It offers several advantages, including cost-effectiveness, high yields,, precious control over the production process. As an emerging family of 2D materials, elemental 2D materials (Xenes) have shown great potential in various applications such as electronics, catalysts, biochemistry,, sensing technologies due to their exceptional/exotic properties such as large surface area, tunable band gap,, high carrier mobility. In this review, we provide a comprehensive overview of the current state-of-the-art in wet-chemical synthesis of Xenes including tellurene, bismuthene, antimonene, phosphorene,, arsenene. The current solvent compositions, process parameters utilized in wet-chemical synthesis, their effects on the thickness, stability of the resulting Xenes are also presented. Key factors considered involves ligands, precursors, surfactants, reaction time, temperature. Finally, we highlight recent advances, existing challenges in the current application of wet-chemical synthesis for Xenes production, provide perspectives on future improvement.

S-induced Phase Change Forming In2 O3 /In2 S3 Heterostructure for Photoelectrochemical Glucose Sensor.

In the past several decades, Photoelectrochemical (PEC) sensing still remains a great challenge to design highly-efficient semiconductor photocatalysts via a facile method. It is of much importance to design and synthesize various novel nanostructured sensing materials for further improving the response performance. Herein, we present an In2 O3 /In2 S3 heterostructure obtained by combining microwave assisted hydrothermal method with S-induced phase change, whose energy band and electronic structure could be adjusted by changing the S content. Combining theoretical calculation and spectroscopic techniques, the introduction of sulfur was proved to produce multifunctional interfaces, inducing the change of phase, oxygen vacancies and band gap, which accelerates the separation of photoexcited carriers and reduces their recombination, improving the electronic injection efficiency around the interface of In2 O3 /In2 S3 . As anticipated, an enhanced glucose response performance with a photocurrent of 0.6 mA cm-2 , a linear range of 0.1-1 mM and a detection limit as low as 14.5 µM has been achieved based on the In2 O3 /In2 S3 heterostructure, which is significant superior over its pure In2 O3 and S-doped In2 O3 counterparts. This efficient interfacial strategy may open a new route to manipulate the electrical structure, and energy band structure regulation of sensing material to improve the performance of photoelectrodes for PEC.

Tensile Strain-Mediated Spinel Ferrites Enable Superior Oxygen Evolution Activity.

Exploring efficient strategies to overcome the performance constraints of oxygen evolution reaction (OER) electrocatalysts is vital for electrocatalytic applications such as H2O splitting, CO2 reduction, N2 reduction, etc. Herein, tunable, wide-range strain engineering of spinel oxides, such as NiFe2O4, is proposed to enhance the OER activity. The lattice strain is regulated by interfacial thermal mismatch during the bonding process between thermally expanding NiFe2O4 nanoparticles and the nonexpanding carbon fiber substrate. The tensile lattice strain causes energy bands to flatten near the Fermi level, lowering eg orbital occupancy, effectively increasing the number of electronic states near the Fermi level, and reducing the pseudoenergy gap. Consequently, the energy barrier of the rate-determining step for strained NiFe2O4 is reduced, achieving a low overpotential of 180 mV at 10 mA/cm2. A total water decomposition voltage range of 1.52-1.56 V at 10 mA/cm2 (without iR correction) was achieved in an asymmetric alkaline electrolytic cell with strained NiFe2O4 nanoparticles, and its robust stability was verified with a voltage retention of approximately 99.4% after 100 h. Furthermore, the current work demonstrates the universality of tuning OER performance with other spinel ferrite systems, including cobalt, manganese, and zinc ferrites.

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.

Reversible Semimetal-Semiconductor Transition of Unconventional-Phase WS2 Nanosheets.

Phase transition with band gap modulation of materials has gained intensive research attention due to its various applications, including memories, neuromorphic computing, and transistors. As a powerful strategy to tune the crystal phase of transition-metal dichalcogenides (TMDs), the phase transition of TMDs provides opportunities to prepare new phases of TMDs for exploring their phase-dependent property, function, and application. However, the previously reported phase transition of TMDs is mainly irreversible. Here, we report a reversible phase transition in the semimetallic 1T'-WS2 driven by proton intercalation and deintercalation, resulting in a newly discovered semiconducting WS2 with a novel unconventional phase, denoted as the 1T'd phase. Impressively, an on/off ratio of >106 has been achieved during the phase transition of WS2 from the semimetallic 1T' phase to the semiconducting 1T'd phase. Our work not only provides a unique insight into the phase transition of TMDs via proton intercalation but also opens up possibilities to tune their physicochemical properties for various applications.

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.

Interfacial Microstructure and Mechanical Properties of 1Cr18Ni9Ti/1Cr21Ni5Ti Stainless Steel Joints Brazed with Mn-Based Brazing Filler.

The problem of stainless steel brazing is still the focus of scientific research. In this work, the Mn-based brazing filler was used to braze 1Cr18Ni9Ti and 1Cr21Ni5Ti stainless steel. The typical microstructure of the 1Cr18Ni9Ti/1Cr21Ni5Ti joint was analyzed in detail, and the interface structure of the joint was determined to be 1Cr18Ni9Ti/Mn(s, s)/1Cr21Ni5Ti. The brazing temperature and holding time were shown to have a great influence on the microstructure of the brazed joint. The tensile strength of brazed joints first increased and then decreased with the rising of the brazing temperature and the holding time. The maximum tensile strength was 566 MPa when the joints were brazed at 1125 °C for 15 min. The diffusion of Mn and Cr was an important factor affecting the quality of the joints. The diffusion distances of Mn and Cr at different brazing temperatures and holding times were measured, and the diffusion activation energy and diffusion coefficient were achieved by the Arrhenius equation.

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.

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.

Atomic-scale imaging of CH3NH3PbI3 structure and its decomposition pathway.

Understanding the atomic structure and structural instability of organic-inorganic hybrid perovskites is the key to appreciate their remarkable photoelectric properties and understand failure mechanism. Here, using low-dose imaging technique by direct-detection electron-counting camera in a transmission electron microscope, we investigate the atomic structure and decomposition pathway of CH3NH3PbI3 (MAPbI3) at the atomic scale. We successfully image the atomic structure of perovskite in real space under ultra-low electron dose condition, and observe a two-step decomposition process, i.e., initial loss of MA+ followed by the collapse of perovskite structure into 6H-PbI2 with their critical threshold doses also determined. Interestingly, an intermediate phase (MA0.5PbI3) with locally ordered vacancies can robustly exist before perovskite collapses, enlightening strategies for prevention and recovery of perovskite structure during the degradation. Associated with the structure evolution, the bandgap gradually increases from ~1.6 eV to ~2.1 eV. In addition, it is found that C-N bonds can be readily destroyed under irradiation, releasing NH3 and HI and leaving hydrocarbons. These findings enhance our understanding of the photoelectric properties and failure mechanism of MAPbI3, providing potential strategies into material optimization.

All-in-One Sulfur Host: Smart Controls of Architecture and Composition for Accelerated Liquid-Solid Redox Conversion in Lithium-Sulfur Batteries.

The development of Li-S batteries (LSBs) is largely impeded by sluggish redox kinetics and notorious polysulfide shuttling. Herein, hierarchical MoC@Ni-NCNT arrays are reported as a multifunctional sulfur host in Li-S batteries, which comprised a flexible carbon fiber cloth substrate decorated with vertical MoC porous nanorods rooted by interconnected nitrogen-doped carbon nanotubes (NCNTs). In the designed host, the inner MoC porous backbone (composed of nanoparticles) along with the in situ-grafted interwoven NCNT shell can greatly maximize the host-guest interactive surface for homogeneous sulfur dispersion, thus realizing decent high-sulfur-loading performance. Ni nanoparticles, encapsulated within NCNTs in the outer shell, act as strong chemical-anchoring centers effectively trap-escaped polysulfides and propel the bidirectional sulfur transformation kinetics. In merit of sufficient adsorption and catalytic sites, the cell configured with the MoC@Ni-NCNT cathode delivers not only high capacity (1421 mA h g-1 at 0.1 C) but also superior rate performance and ultralong lifespan. The cell can still achieve a superb areal capacity of 6.1 mA h cm2 under an increased sulfur loading up to 6 mg cm-2. This work could open a new avenue for the construction of a multifunctional cathode for high-performance LSBs.

Self-Assembly Lightweight Honeycomb-Like Prussian Blue Analogue on Cu Foam for Lithium Metal Anode.

As a next-generation anode material for lithium batteries, Li metal anode suffers from inherent drawbacks such as infinite volume expansion and uneven Li plating/stripping. Herein, we propose a lightweight lithiophilic Prussian blue analogue (PBA) with honeycomb-like structure on Cu foam by self-assembly method to address these issues. The unique honeycomb-like architecture could provide enlarged surface areas and abundant deposition sites for homogenizing Li+ flux during Li plating. Consequently, the elaborate PBA-decorated Cu foam current collector enables long-term (1800 h) reversible plating/stripping behavior and an observably improved Coulombic efficiency (98.3% after 350 cycles). The concept of the direct self-assembly synthesis method on metal foam provides new insights into the design of a lightweight 3-dimensional current collector for Li metal anode.

Bioinspired Metal-Intermetallic Laminated Composites for the Fabrication of Superhydrophobic Surfaces with Responsive Wettability.

Hundreds of copper and titanium foils were applied to prepare biomimetic metal-intermetallic laminated composites by diffusion bonding. The cross sections of the obtained diffusion bonded bulks were etched selectively with FeCl3 solution to get regular microarray structures. This kind of microstructure was controlled accurately and promptly by simple parameter adjustment. The etched surfaces were modified with 1-dodecanethiol, and the water contact angles (WCAs) were measured. The relationship between the microstructure and wettability of the achieved material was discussed, and the reason for the anisotropic wettability was also analyzed. Then etched surfaces were anodized in different electrolyte solutions to obtain different nanostructures. The morphology and chemical compositions of the surfaces were analyzed. The surfaces with CuO nanostructures by modification show superhydrophobicity with self-cleaning, on which the WCA and water sliding angle are 160.9° and 0.8°, respectively. The surfaces with TiO2 nanostructures without modification show ultraviolet light-responsive wettability. After modification with 11-mercaptoundecanoic acid and 1-decanethiol, the surfaces also exhibit pH-responsive wettability. The superhydrophobic surfaces with responsive wettability have potential applications in biotechnology and microfluidics.

Antimony nanocrystals self-encapsulated within bio-oil derived carbon for ultra-stable sodium storage.

Integrating carbon-coating and nanostructuring has been considered as the most promising strategy to accommodate the dramatic volume expansion represented by high-capacity antimony (Sb) upon sodiation. Suitable coating source and synthetic strategy that are both economical and strong are yet to be explored. In this regard, by using renewable bio-oil as carbon source and self-wrapping precursor, robust Sb@C composite anode with Sb nanoparticles homogeneously impregnated into the cross-linked 2D ultrathin carbon nanosheets is developed via a facile NaCl template-assisted self-assembly and followed carbothermal reduction method. Such judiciously crafted interconnected macroporous framework can mitigate of mechanical stress and alleviate the volume change of inner Sb, guaranteeing high-performance sodium-ion battery anode. At a current density of 0.1 A g-1, ultrahigh reversible capacity of 520 mAh g-1 can be achieved. Notably, a stable capacity of 391 mAh g-1 is even retained after 500 cycles at 1 A g-1. Such a facile and cost-effective synthetic method is promising for high-performance sodium-ion batteries.

Surface activation towards manganese dioxide nanosheet arrays via plasma engineering as cathode and anode for efficient water splitting.

Developing high-efficiency, low-cost electrocatalysts for water splitting is important but challenging. Two-dimensional nanosheet manganese dioxide (MnO2) arrays are promising candidates for the design and development of advanced catalysts because of their large surface area. Here, a feasible solution to improve the catalytic activity of MnO2 materials via decorating the active sites on the surface is proposed. With the help of plasma engineering, we successfully enabled surface activity of the MnO2 nanosheets by decorating P or Fe species together with rich vacancies on the surface. The decorated P (P-MnO2) or Fe (Fe-MnO2) species were highly beneficial for the absorption of protons and OH- respectively, and rich oxygen vacancies induced the formation of stable Mn3+, which contributed to electron and charge transfer. Thus, increased electrochemically active specific areas, accelerated charge transfer, and a proper surface electronic structure could be achieved. On the basis of this activation strategy, the fabricated P-MnO2 and Fe-MnO2 showed excellent catalytic performance for the hydrogen evolution and oxygen evolution reactions. To our knowledge, the performance of P-MnO2 and Fe-MnO2 outperformed most MnO2-based electrocatalysts in the field of electrocatalytic water splitting. Surface activation of two-dimensional MnO2 materials by decorating active species via plasma treatment can provide a feasible route for modulating the performance of earth-abundant electrocatalysts for practical applications.

Direct Observation of Li Migration into V5S8: Order to Antisite Disorder Intercalation Followed by the Topotactic-Based Conversion Reaction.

Two-dimensional transition-metal dichalcogenides hold great potential in rechargeable lithium-ion batteries. Their electrochemical properties are closely related to the structural evolutions during lithium-ion migration. Understanding these migration/reaction mechanisms is important to help improve battery performance. Herein, we report the real-time and atomic-scale observation of phase transitions during the lithiation and delithiation for V5S8 via in situ electron diffraction and high-resolution transmission electron microscopy techniques. We find that the phase transformation proceeds via a sequence of order to antisite disorder intercalation and topotactic-based conversion reaction. During the intercalation reaction, the lithium ion destroys the orderings of the interstitial V with the formation of Li/V antisite. Such a reaction is found to be reversible, i.e., the extraction of lithium from LixV5S8 leads to the recovery of V orderings. The conversion reaction involves heterogeneous nucleation of Li2S with 3-20 nm nanodomains, which maintain the crystallographic integrity with LixV5S8. These findings elucidate the complex interactions between the lithium ion and host V5S8 during ionic migration in solids, which should be helpful in understanding the relationship between phase transformation kinetics and battery performance.

Rationally designed C/Co9S8@SnS2 nanocomposite as a highly efficient anode for lithium-ion batteries.

Nanostructured transition metal sulfides are promising anode materials for lithium-ion batteries. Nevertheless, it is still a great challenge to prepare capacity-improved electrodes without reducing their rate capability and cycle stability. In this paper, we present a C/Co9S8@SnS2 composite material by loading SnS2 nanocrystals onto MOF-derived C/Co9S8 nanostructures. The C/Co9S8@SnS2 composite has multiple active sites to store lithium ions. The specific capacity reaches 3.1 mAh cm-2 when the current density is 0.224 mA cm-2. The asynchronous electrochemical reaction between Co9S8 and SnS2 offsets the volume expansion of the anode material. Meanwhile, the compact adhesion of carbon layers on the interfaces suppresses the destruction of the anode during the charging-discharging processes. Consequently, the synthesized electrode presents favorable capacity with high current density or under long-term cycling conditions. The prepared battery has a reversible specific capacity of 0.452 mAh cm-2 and a coulomb efficiency of 99.7% after 500 cycles with a high current density of 2.24 mA cm-2. The research results obtained in this work provides a feasible strategy to improve the performance of electrodes systematically.