Single-Atom Engineering to Ignite 2D Transition Metal Dichalcogenide Based Catalysis: Fundamentals, Progress, and Beyond.

Single-atom catalysis has been recognized as a pivotal milestone in the development history of heterogeneous catalysis by virtue of its superior catalytic performance, ultrahigh atomic utilization, and well-defined structure. Beyond single-atom protrusions, two more motifs of single-atom substitutions and single-atom vacancies along with synergistic single-atom motif assemblies have been progressively developed to enrich the single-atom family. On the other hand, besides traditional carbon material based substrates, a wide variety of 2D transitional metal dichalcogenides (TMDs) have been emerging as a promising platform for single-atom catalysis owing to their diverse elemental compositions, variable crystal structures, flexible electronic structures, and intrinsic activities toward many catalytic reactions. Such substantial expansion of both single-atom motifs and substrates provides an enriched toolbox to further optimize the geometric and electronic structures for pushing the performance limit. Concomitantly, higher requirements have been put forward for synthetic and characterization techniques with related technical bottlenecks being continuously conquered. Furthermore, this burgeoning single-atom catalyst (SAC) system has triggered serial scientific issues about their changeable single atom-2D substrate interaction, ambiguous synergistic effects of various atomic assemblies, as well as dynamic structure-performance correlations, all of which necessitate further clarification and comprehensive summary. In this context, this Review aims to summarize and critically discuss the single-atom engineering development in the whole field of 2D TMD based catalysis covering their evolution history, synthetic methodologies, characterization techniques, catalytic applications, and dynamic structure-performance correlations. In situ characterization techniques are highlighted regarding their critical roles in real-time detection of SAC reconstruction and reaction pathway evolution, thus shedding light on lifetime dynamic structure-performance correlations which lay a solid theoretical foundation for the whole catalytic field, especially for SACs.

Morphotropic Phase Boundary in Polarized Organic Piezoelectric Materials.

Designing the morphotropic phase boundary (MPB) has been the most sought-after approach to achieve high piezoelectric performance of piezoelectric materials. However, MPB has not yet been found in the polarized organic piezoelectric materials. Here, we discover MPB with biphasic competition of ß and 3/1-helical phases in the polarized piezoelectric polymer alloys (PVTC-PVT) and demonstrate a mechanism to induce MPB using the compositionally tailored intermolecular interaction. Consequently, PVTC-PVT exhibits a giant quasistatic piezoelectric coefficient of >32 pC/N while maintaining a low Young's modulus of 182 MPa, with a record-high figure of merit of piezoelectricity modulus of about 176 pC/(N·GPa) among all piezoelectric materials.

Omnibearing Interpretation of External Ions Passivated Ion Migration in Mixed Halide Perovskites.

Fundamental understanding of ion migration inside perovskites is of vital importance for commercial advancements of photovoltaics. However, the mechanism for external ions incorporation and its effect on ion migration remains elusive. Herein, taking K+ and Cs+ co-incorporated mixed halide perovskites as a model, the impact of external ions on ion migration behavior has been interpreted via multiple dimensional characterization aspects. The space-effect on phase segregation inhibition has been revealed by the photoluminescence evolution and in situ dynamic cathodoluminescence behaviors. The plane-effect on current suppression along grain boundary has been evidenced via visualized surface current mapping, local current hysteresis, and time-resolved current decay. And the point-effect on activation energy incremental for individual ions has been also probed by cryogenic electronic quantification. All these results sufficiently demonstrate the passivated ion migration results in the eventually improved phase stability of perovskite, of which the origin lies in various ion migration energy barriers.

Identifying and Interpreting Geometric Configuration-Dependent Activity of Spinel Catalysts for Water Reduction.

The catalytic activity of transition metal-based catalysts is overwhelmingly dependent on the geometric configuration. Identification and interpretation of different geometric configurations' contributions to catalytic activity plays a pivotal role in catalytic performance elevation. Spinel structured AB2X4, consisting of tetrahedral (A2+-X)Td and octahedral (B3+-X)Oh geometric configurations, is a prototypical category of multi-geometric-configuration featured catalysts. However, it is still under debate about the predominant geometric configuration responsible for spinel catalyst activity, and the mechanistic origin of specific activity discrepancy among varied geometric configurations also remains ambiguous. Herein, CoTd2+ and CoOh3+ in Co3O4 are replaced by catalytically inert Zn2+ and Al3+ to yield ZnCo2O4 and CoAl2O4, respectively, thus ensuring the manipulable exposure of monotypic active configurations. By means of pulse voltammetry and in situ extended X-ray absorption fine structure, (Co3+-O)Oh is identified to be dominant for alkaline HER. In-depth theoretical investigation in combination with X-ray absorption spectroscopy further interprets the synergistic effect between Co and O sites in (Co3+-O)Oh configuration on water reduction kinetics upon both water dissociation and hydrogen desorption steps. Furthermore, specific facet dependence of catalytic activity is also deciphered based on precise facet exposure identification and serial theoretical analysis. This work unambiguously figures out the subtle geometric configuration dependence of spinel catalyst activity for water reduction and highlights the synergistic relationship among different components confined in geometric configuration, thereby shedding new light on the rational design of advanced catalysts from the atomic level of geometric configuration optimization.

Single-Atom Vacancy Defect to Trigger High-Efficiency Hydrogen Evolution of MoS2.

Defect engineering is widely applied in transition metal dichalcogenides (TMDs) to achieve electrical, optical, magnetic, and catalytic regulation. Vacancies, regarded as a type of extremely delicate defect, are acknowledged to be effective and flexible in general catalytic modulation. However, the influence of vacancy states in addition to concentration on catalysis still remains vague. Thus, via high throughput calculations, the optimized sulfur vacancy (S-vacancy) state in terms of both concentration and distribution is initially figured out among a series of MoS2 models for the hydrogen evolution reaction (HER). In order to realize it, a facile and mild H2O2 chemical etching strategy is implemented to introduce homogeneously distributed single S-vacancies onto the MoS2 nanosheet surface. By systematic tuning of the etching duration, etching temperature, and etching solution concentration, comprehensive modulation of the S-vacancy state is achieved. The optimal HER performance reaches a Tafel slope of 48 mV dec-1 and an overpotential of 131 mV at a current density of 10 mA cm-2, indicating the superiority of single S-vacancies over agglomerate S-vacancies. This is ascribed to the more effective surface electronic structure engineering as well as the boosted electrical transport properties. By bridging the gap, to some extent, between precise design from theory and practical modulation in experiments, the proposed strategy extends defect engineering to a more sophisticated level to further unlock the potential of catalytic performance enhancement.

Atomic-Thin ZnO Sheet for Visible-Blind Ultraviolet Photodetection.

The atomic-thin 2D semiconductors have emerged as plausible candidates for future optoelectronics with higher performance in terms of the scaling process. However, currently reported 2D photodetectors still have huge shortcomings in ultraviolet and especially visible-blind wavelengths. Here, a simple and nontoxic surfactant-assisted synthesis strategy is reported for the controllable growth of atomically thin (1.5 to 4 nm) ZnO nanosheets with size ranging from 3 to 30 µm. Benefit from the short carbon chains and the water-soluble ability of sodium dodecyl sulfate (SDS), the synthesized ZnO nanosheets possess high crystal quality and clean surface, leading to good compatibility with traditional micromanufacturing technology and high sensitivity to UV light. The photodetectors constructed with ZnO demonstrate the highest responsivity (up to 2.0 × 104 A W-1 ) and detectivity (D* = 6.83 × 1014 Jones) at a visible-blind wavelength of 254 nm, and the photoresponse speed is optimized by the 400 °C annealing treatment (τR  = 3.97 s, τD  = 5.32 s), thus the 2D ZnO can serve as a promising material to fill in the gap for deep-UV photodetection. The method developed here opens a new avenue to controllably synthesize 2D nonlayered materials and accelerates their applications in high-performance optoelectronic devices.

Graphdiyne: Bridging SnO2 and Perovskite in Planar Solar Cells.

The matching of charge transport layer and photoactive layer is critical in solar energy conversion devices, especially for planar perovskite solar cells based on the SnO2 electron-transfer layer (ETL) owing to its unmatched photogenerated electron and hole extraction rates. Graphdiyne (GDY) with multi-roles has been incorporated to maximize the matching between SnO2 and perovskite regarding electron extraction rate optimization and interface engineering towards both perovskite crystallization process and subsequent photovoltaic service duration. The GDY doped SnO2 layer has fourfold improved electron mobility due to freshly formed C-O σ bond and more facilitated band alignment. The enhanced hydrophobicity inhibits heterogeneous perovskite nucleation, contributing to a high-quality film with diminished grain boundaries and lower defect density. Also, the interfacial passivation of Pb-I anti-site defects has been demonstrated via GDY introduction.

Nonenzymatic Glucose Sensor Based on In Situ Reduction of Ni/NiO-Graphene Nanocomposite.

Ni/NiO nanoflower modified reduced graphene oxide (rGO) nanocomposite (Ni/NiO-rGO) was introduced to screen printed electrode (SPE) for the construction of a nonenzymatic electrochemical glucose biosensor. The Ni/NiO-rGO nanocomposite was synthesized by an in situ reduction process. Graphene oxide (GO) hybrid Nafion sheets first chemical adsorbed Ni ions and assembled on the SPE. Subsequently, GO and Ni ions were reduced by hydrazine hydrate. The electrochemical properties of such a Ni/NiO-rGO modified SPE were carefully investigated. It showed a high activity for electrocatalytic oxidation of glucose in alkaline medium. The proposed nonenzymatic sensor can be utilized for quantification of glucose with a wide linear range from 29.9 µM to 6.44 mM (R = 0.9937) with a low detection limit of 1.8 µM (S/N = 3) and a high sensitivity of 1997 µA/mM∙cm-2. It also exhibited good reproducibility as well as high selectivity.

In situ transmission electron microscopy investigation on fatigue behavior of single ZnO wires under high-cycle strain.

The fatigue behavior of ZnO nanowires (NWs) and microwires was systematically investigated with in situ transmission electron microscopy electromechanical resonance method. The elastic modulus and mechanical quality factors of ZnO wires were obtained. No damage or failure was found in the intact ZnO wires after resonance for about 10(8)-10(9) cycles, while the damaged ZnO NW under electron beam (e-beam) irradiation fractured after resonance for seconds. The research results will provide a useful guide for designing, fabricating, and optimizing electromechanical nanodevices based on ZnO nanomaterials, as well as future applications.

In-Sensor Tactile Fusion and Logic for Accurate Intention Recognition.

Touch control intention recognition is an important direction for the future development of human-machine interactions (HMIs). However, the implementation of parallel-sensing functional modules generally requires a combination of different logical blocks and control circuits, which results in regional redundancy, redundant data, and low efficiency. Here, a location-and-pressure intelligent tactile sensor (LPI tactile sensor) unprecedentedly combined with sensing, computing, and logic is proposed, enabling efficient and ultrahigh-resolution action-intention interaction. The LPI tactile sensor eliminates the need for data transfer among the functional units through the core integration design of the layered structure. It actuates in-sensor perception through feature transmission, fusion, and differentiation, thereby revolutionizing the traditional von Neumann architecture. While greatly simplifying the data dimensionality, the LPI tactile sensor achieves outstanding resolution sensing in both location (<400 µm) and pressure (75 Pa). Synchronous feature fusion and decoding support the high-fidelity recognition of action and combinatorial logic intentions. Benefiting from location and pressure synergy, the LPI tactile sensor demonstrates robust privacy as an encrypted password device and interaction intelligence through pressure enhancement. It can recognize continuous touch actions in real time, map real intentions to target events, and promote accurate and efficient intention-driven HMIs.

The dynamic surface evolution of halide perovskites induced by external energy stimulation.

Tracking the dynamic surface evolution of metal halide perovskite is crucial for understanding the corresponding fundamental principles of photoelectric properties and intrinsic instability. However, due to the volatility elements and soft lattice nature of perovskites, several important dynamic behaviors remain unclear. Here, an ultra-high vacuum (UHV) interconnection system integrated by surface-sensitive probing techniques has been developed to investigate the freshly cleaved surface of CH3NH3PbBr3  in situ under given energy stimulation. On this basis, the detailed three-step chemical decomposition pathway of perovskites has been clarified. Meanwhile, the evolution of crystal structure from cubic phase to tetragonal phase on the perovskite surface has been revealed under energy stimulation. Accompanied by chemical composition and crystal structure evolution, electronic structure changes including energy level position, hole effective mass, and Rashba splitting have also been accurately determined. These findings provide a clear perspective on the physical origin of optoelectronic properties and the decomposition mechanism of perovskites.

Reduced graphene oxide-functionalized high electron mobility transistors for novel recognition pattern label-free DNA sensors.

We designed and constructed reduced graphene oxide (rGO) functionalized high electron mobility transistor (HEMT) for rapid and ultra-sensitive detection of label-free DNA in real time. The micrometer sized rGO sheets with structural defects helped absorb DNA molecules providing a facile and robust approach to functionalization. DNA was immobilized onto the surface of HEMT gate through rGO functionalization, and changed the conductivity of HEMT. The real time monitor and detection of DNA hybridization by rGO functionalized HEMT presented interesting current responses: a "two steps" signal enhancement in the presence of target DNA; and a "one step" signaling with random DNA. These two different recognition patterns made the HEMT capable of specifically detecting target DNA sequence. The working principle of the rGO functionalized HEMT can be demonstrated as the variation of the ambience charge distribution. Furthermore, the as constructed DNA sensors showed excellent sensitivity of detect limit at 0.07 fM with linear detect range from 0.1 fM to 0.1 pM. The results indicated that the HEMT functionalized with rGO paves a new avenue to design novel electronic devices for high sensitive and specific genetic material assays in biomedical applications.

Roles of Low-Dimensional Nanomaterials in Pursuing Human-Machine-Thing Natural Interaction.

A wide variety of low-dimensional nanomaterials with excellent properties can meet almost all the requirements of functional materials for information sensing, processing, and feedback devices. Low-dimensional nanomaterials are becoming the star of hope on the road to pursuing human-machine-thing natural interactions, benefiting from the breakthroughs in precise preparation, performance regulation, structural design, and device construction in recent years. This review summarizes several types of low-dimensional nanomaterials commonly used in human-machine-thing natural interactions and outlines the differences in properties and application areas of different materials. According to the sequence of information flow in the human-machine-thing interaction process, the representative research progress of low-dimensional nanomaterials-based information sensing, processing, and feedback devices is reviewed and the key roles played by low-dimensional nanomaterials are discussed. Finally, the development trends and existing challenges of low-dimensional nanomaterials in the field of human-machine-thing natural interaction technology are discussed.

Deciphering Vacancy Defect Evolution of 2D MoS2 for Reliable Transistors.

Two-dimensional (2D) MoS2 is an excellent candidate channel material for next-generation integrated circuit (IC) transistors. However, the reliability of MoS2 is of great concern due to the serious threat of vacancy defects, such as sulfur vacancies (VS). Evaluating the impact of vacancy defects on the service reliability of MoS2 transistors is crucial, but it has always been limited by the difficulty in systematically tracking and analyzing the changes and effects of vacancy defects in the service environment. Here, a simulated initiator is established for deciphering the evolution of vacancy defects in MoS2 and their influence on the reliability of transistors. The results indicate that VS below 1.3% are isolated by slow enrichment during initiation. Over 1.3% of VS tend to enrich in pairs and over 3.5% of the enriched VS easily evolve into nanopores. The enriched VS with electron doping in the channel cause the threshold voltage (Vth) negative drift approaching 6 V, while the expanded nanopores initiate the Vth roll-off and punch-through of transistors. Finally, sulfur steam deposition has been proposed to constrain VS enrichment, and reliable MoS2 transistors are constructed. Our research provides a new method for deciphering and identifying the impact of defects.

Conformal Human-Machine Integration Using Highly Bending-Insensitive, Unpixelated, and Waterproof Epidermal Electronics Toward Metaverse.

Efficient and flexible interactions require precisely converting human intentions into computer-recognizable signals, which is critical to the breakthrough development of metaverse. Interactive electronics face common dilemmas, which realize high-precision and stable touch detection but are rigid, bulky, and thick or achieve high flexibility to wear but lose precision. Here, we construct highly bending-insensitive, unpixelated, and waterproof epidermal interfaces (BUW epidermal interfaces) and demonstrate their interactive applications of conformal human-machine integration. The BUW epidermal interface based on the addressable electrical contact structure exhibits high-precision and stable touch detection, high flexibility, rapid response time, excellent stability, and versatile "cut-and-paste" character. Regardless of whether being flat or bent, the BUW epidermal interface can be conformally attached to the human skin for real-time, comfortable, and unrestrained interactions. This research provides promising insight into the functional composite and structural design strategies for developing epidermal electronics, which offers a new technology route and may further broaden human-machine interactions toward metaverse.

Comparison of biochemical composition, nutritional quality, and metals concentrations between males and females of three different Crassostrea sp.

Gametogenesis can significantly affect the biochemical composition of oysters, but little research on the difference between sexes. Therefore, we conducted the first in-depth study on the composition differences between males and females of three different Crassostrea sp.. The results showed that females had higher glycogen, lipid, Cu and Zn contents than males, while males had higher protein and taurine contents than females at maturity, which might be related to special meiosis pattern of eggs and less energy was required for female gametogenesis. In addition, both males and females had well-balanced essential amino acid compositions. The omega-3: omega-6 (n-3: n-6) ratio of males was significantly higher than that of females, indicating that the nutritional quality of males was higher. These results provide a reliable and refined theoretical and research basis for revealing the nutritional quality, extracting beneficial ingredients, and developing functional food of Crassostrea sp., and provide data support for the sex-regulated breeding of oysters.

Boosting Charge Utilization in Self-Powered Photodetector for Real-Time High-Throughput Ultraviolet Communication.

Ultraviolet (UV) communication is a cutting-edge technology in communication battlefields, and self-powered photodetectors as their optical receivers hold great potential. However, suboptimal charge utilization has largely limited the further performance enhancement of self-powered photodetectors for high-throughput communication application. Herein, a self-powered Ti3 C2 Tx -hybrid poly(3,4 ethylenedioxythiophene):poly-styrene sulfonate (PEDOT:PSS)/ZnO (TPZ) photodetector is designed, which aims to boost charge utilization for desirable applications. The device takes advantage of photothermal effect to intensify pyro-photoelectric effect as well as the increased conductivity of the PEDOT:PSS, which significantly facilitated charge separation, accelerated charge transport, and suppressed interface charge recombination. Consequently, the self-powered TPZ photodetector exhibits superior comprehensive performance with high responsivity of 12.3 mA W-1 and fast response time of 62.2 µs, together with outstanding reversible and stable cyclic operation. Furthermore, the TPZ photodetector has been successfully applied in an integrated UV communication system as the self-powered optical receiver capable of real-time high-throughput information transmission with ASCII code under 9600 baud rate. This work provides the design insight of highly performing self-powered photodetectors to achieve high-efficiency optical communication in the future.

Effect of surface modifications on ZnO nanorod arrays electrode for dye-sensitized solar cells.

High quality, large area and well-oriented ZnO nanorod arrays electrodes were successfully synthesized on conductive transparent oxide substrates by low-temperature hydrothermal methods for dye-sensitized solar cells. Aiming at getting further enhancement and study the effect of the surface modification on cell performance, ZnO thin film and ZnO nanoparticles are carried out to modify the as-grown ZnO nanorod arrays. The morphology, structure and photoluminescence property of the modified ZnO electrodes are characterized in detail. Furthermore, the I-V characterization result shows that these modification methods have distinct influences on the performance of the cell based on ZnO nanorod arrays electrode. The overall conversion efficiency can be optimized by choosing the suitable modification route.

Study on the electron emission properties of ZnO nanorod arrays on different substrates.

Large area well-aligned ZnO nanorod arrays on different substrates were synthesized by hydrothermal methods. The electron emission properties of the ZnO nanorod arrays on different substrates were investigated under both direct current (DC) and pulse electric fields. Owing to the excellent conductivity of substrates, the array on stainless steel substrate had better electron emission properties than that on silicon substrate. Under the DC and pulse electric fields, the electron emission of arrays had different production mechanisms which were pure field emission and plasma-induced emission respectively. During the plasma-induced emission, the plasma formed on the array surface, and the maximum emission current density of arrays on stainless steel was 118.87 A/cm2. The plasma-induced emission of ZnO nanorod arrays were always distributed uniformly. In this work, the results show that the ZnO nanorod arrays are expected to be applied to different electronic devices as electron beam sources under different electric fields.