Insights into the Origin of Activity Enhancement via Tuning Electronic Structure of Cu2O towards Electrocatalytic Ammonia Synthesis.

The insight of the activity phase and reaction mechanism is vital for developing high-performance ammonia synthesis electrocatalysts. In this study, the origin of the electronic-dependent activity for the model Cu2O catalyst toward ammonia electrosynthesis with nitrate was probed. The modulation of the electronic state and oxygen vacancy content of Cu2O was realized by doping with halogen elements (Cl, Br, I). The electrocatalytic experiments showed that the activity of the ammonia production depends strongly on the electronic states in Cu2O. With increased electronic state defects in Cu2O, the ammonia synthesis performance increased first and then decreased. The Cu2O/Br with electronic defects in the middle showed the highest ammonia yield of 11.4 g h-1 g-1 at -1.0 V (vs. RHE), indicating that the pattern of change in optimal ammonia activity is consistent with the phenomenon of volcano curves in reaction chemistry. This work highlights a promising route for designing NO3-RR to NH3 catalysts.

Effect of thermal treatment on microcracking characteristics of granite under tensile condition based on bonded-particle model and moment tensor.

It is known that the heterogeneity caused by thermally induced micro-cracks and thermal stress can affect the mechanical behavior of granite. The laboratory-scale tests have the intrinsic limitation of non-repeatability and lack of effective methods to characterize the interaction effect between thermal micro-cracks and thermal stresses. In this study, we demonstrate how advancements in particle bonded model and moment tensor can help better understand the roles of high temperature in weakening granite and thermally induced cracking process in Brazilian test. Our results show that the types of micro-cracks (intergranular, intragranular, and transcrystalline ones) are related to their thermal expansion coefficients of mineralogical compositions. The intergranular tensile micro-cracks are predominant during the heating and heating-cooling processes. An obvious weakening of granite and non-central initiation is associated with the heterogeneity caused by the thermal damage and thermal stress. We also quantitatively evaluate the thermal damage based on orientation distribution, b-value, and nature of the sources, which gives a new microcracking perspective on tensile characteristics subjected to high temperature.

Insect-Scale Biped Robots Based on Asymmetrical Friction Effect Induced by Magnetic Torque.

Multimodal and controllable locomotion in complex terrain is of great importance for practical applications of insect-scale robots. Robust locomotion plays a particularly critical role. In this study, a locomotion mechanism for magnetic robots based on asymmetrical friction effect induced by magnetic torque is revealed and defined. The defined mechanism overcomes the design constraints imposed by both robot and substrate structures, enabling the realization of multimodal locomotion on complex terrains. Drawing inspiration from human walking and running locomotion, a biped robot based on the mechanism is proposed, which not only exhibits rapid locomotion across substrates with varying friction coefficients but also achieves precise locomotion along patterned trajectories through programmed controlling. Furthermore, apart from its exceptional locomotive capabilities, the biped robot demonstrates remarkable robustness in terms of load-carrying and weight-bearing performance. The presented locomotion and mechanism herein introduce a novel concept for designing magnetic robots while offering extensive possibilities for practical applications in insect-scale robotics.

Facile Synthesis of a Multifunctional SnO2 Nanoparticles/Nanosheets Composite for Dye-Sensitized Solar Cells.

Synthesizing SnO2 composite nanostructures via a facile one-step method has been proven to be a great challenge. By adjusting operating variables, such as the reaction solution's pH and solvent type, several SnO2 nanostructures, in particular, a function-matching SnO2 hybrid structure composed of irregular zero-dimensional nanoparticles (NPs) and two-dimensional nanosheets (NSs), could be created. The as-prepared SnO2 composites were then characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscope (SEM), and diffuse reflectance spectroscopy (DRS) to determine their physical properties. Dye-sensitized solar cells (DSCs) constructed with the resultant multifunctional SnO2 NPs/NSs composite exhibited the highest overall power conversion efficiency (PCE) of 5.16% among all products with a corresponding short-circuit current density of 18.6 mA/cm2 and an open-circuit voltage of 0.626 V. The improved performance can be attributed to the combined effects of each component in the composite, i.e., the intentionally introduced nanosheets provide desired electron transport and enhanced light scattering capability, while the nanoparticles retain their large surface area for efficient dye absorption.

Advancing Energy Storage and Catalysis with Novel Nanomaterials.

In the dynamic realm of materials science, novel nanomaterials possess the transformative potential to reshape various industries, ranging from energy storage to catalysis [...].

FeIII Chelated with Humic Acid with Easy Synthesis Conditions and Good Performance as Anode Materials for Lithium-Ion Batteries.

In this work, we prepared a green, cheap material by chelating humic acid with ferric ions (HA-Fe) and used it as an anode material in LIBs for the first time. From the SEM, TEM, XPS, XRD, and nitrogen adsorption-desorption experimental results, it was found that the ferric ion can chelate with humic acid successfully under mild conditions and can increase the surface area of materials. Taking advantage of the chelation between the ferric ions and HA, the capacity of HA-Fe is 586 mAh·g-1 at 0.1 A·g-1 after 1000 cycles. Moreover, benefitting from the chelation effect, the activation degree of HA-Fe (about 8 times) is seriously improved compared with pure HA material (about 2 times) during the change-discharge process. The capacity retention ratio of HA-Fe is 55.63% when the current density increased from 0.05 A·g-1 to 1 A·g-1, which is higher than that of HA (32.55%) and Fe (24.85%). In the end, the storage mechanism of HA-Fe was investigated with ex-situ XPS measurements, and it was found that the C=O and C=C bonds are the activation sites for storage Li ions but have different redox voltages.

Preparation of CuO@humic acid@carbon nanotube composite material using humic acid as a coupling agent and its lithium-ion storage performance.

The conventional Li-ion battery composite electrode material composed of CuO and carbon nanotubes (CNTs) suffer from poor contact between CuO and CNTs. This results in high electrode resistance and poor electrochemical performance. To solve this problem, CuO@humic acid (HA) @CNT anode material with cross-linked network structure was generated by linking CuO and CNT with HA as a coupling agent. For comparison, CuO@HA or CuO@CNT were also prepared in the absence of CNT or HA, respectively. The results showed that CuO@HA@CNT had lower charge transfer resistance, higher conductivity, lithium-ion diffusion coefficient, specific capacity, and rate capability than CuO@HA and CuO@CNT. The specific capacity of the CuO@HA@CNT electrode was significantly better than that of the composite electrode materials of CuO and CNT, which have been prepared by scientists using various methods. Due to the introduction of HA, not only was the uniformly distributed flower-like CuO obtained, but also the specific capacity and rate capability of the electrode material were substantially improved. This study thus provides a good strategy to optimize the capability of transition metal oxide lithium-ion anode materials.

Enhancing the Electrochemical Performance of High Voltage LiNi0.5Mn1.5O4 Cathode Materials by Surface Modification with Li1.3Al0.3Ti1.7(PO4)3/C.

A novel method for surface modification of LiNi0.5Mn1.5O4 (LNMO) was proposed, in which a hybrid layer combined by Li1.3Al0.3Ti1.7(PO4)3 (LATP) and carbon (C) composite on LNMO material were connected by lithium iodide. Structure and morphology analyses illustrated that a higher contact area of active substances was achieved by the LATP/C composite layer without changing the original crystal structure of LNMO. XPS analysis proved that I- promoted the reduction of trace Mn4+, resulting in a higher ion conductivity. Galvanostatic charge-discharge tests exhibited the capacity of the LNMO with 5% LATP/C improved with 35.83% at 25 °C and 95.77% at 50 °C, respectively, compared with the bare after 100 cycles, implying the modification of high-temperature deterioration. EIS results demonstrated that one order of magnitude of improvement of the lithium-ion diffusion coefficient of LATP/C-LNMO was achieved (3.04 × 10-11 S cm-1). In conclusion, the effective low-temperature modification strategy improved the ionic and electronic conductivities of the cathode and suppressed the side reactions of high-temperature treatment.

Synthesis and Characterization of Solution-Processible Donor-Acceptor Electrochromic Conjugated Copolymers Based on Quinoxalino[2',3':9,10]phenanthro[4,5-abc]phenazine as the Acceptor Unit.

Donor-acceptor (D-A) type conjugated polymers are of high interest in the field of electrochromism. In this study, three novel conjugated copolymers (PBPE-1, PBPE-2 and PBPE-3) based on quinoxalino[2',3':9,10]phenanthro[4,5-abc]phenazine (A) as the acceptor unit and 4,8-bis((2-octyldodecyl)oxy)benzo[1,2-b:4,5-b']dithiophene (D1) and 3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine (ProDOT-decyl2, D2) as the donor units with different donor-to-acceptor ratios were successfully synthesized through Stille coupling polymerization. The polymers were then characterized by cyclic voltammetry (CV), fourier transform infrared (FT-IR) spectoscopy, X-ray photoelectron spectroscopy (XPS), spectroelectrochemistry, thermogravimetry (TG), electrochromic switching and colorimetry. Optical band gap values were calculated as 1.99 eV, 2.02 eV and 2.03 eV, respectively. The three copolymers have good solubility, distinct redox peaks, wide absorption spectra, good thermal stabilities, bright color changes and significant electrochromic switching properties. Compared to the other two copolymers, the PBPE-3 film exhibited high coloration efficiency values of 513 cm2·C-1 at 504 nm and 475 cm2·C-1 at 1500 nm. The films have the advantage of exhibiting cathodic and anodic coloration.

Efficient photocatalytic hydrogen evolution: Linkage units engineering in triazine-based conjugated porous polymers.

Conjugated porous polymers (CPPs) have been widely reported as promising photocatalysts. However, the realization of powerful photocatalytic hydrogen production performance still benefits from the rational design of molecular frameworks and the appropriate choice of building monomers. Herein, we synthesized two novel conjugated porous polymers (CPPs) by copolymerizing pyrene and 1,3,5-triazine building blocks. It is found that minor structural changes in the peripheral groups of the triazine units can greatly affect the photocatalytic activity of the polymers. Compared with the phenyl-linkage unit, the thiophene-linkage unit can give CPP a wider absorption range of visible light, a narrower band gap, a higher transmission and separation efficiency of photo-generated carriers (electrons/holes), and a better interface contact with the photocatalytic reaction solution. The catalyst containing thiophene-triazine (ThPy-CPP) has an efficient photocatalytic hydrogen evolution rate of 21.65 and 16.69 mmol g-1h-1 under full-arc spectrum and visible light without the addition of a Pt co-catalyst, respectively, much better than the one containing phenyl-triazine (PhPy-CPP, only 5.73 and 3.48 mmol g-1h-1). This study provides a promising direction to design and construct highly efficient, cost-effective CPP-based photocatalysts, for exploring the application of noble metal-free catalysts in photocatalytic hydrogen evolution.

Enhanced photocatalytic hydrogen evolution activity of co-catalyst free S-scheme polymer heterojunctions via ultrasonic assisted reorganization in solvent.

In this work, two donor-acceptor linear conjugated polymers were designed and synthesized based on thianthrene-5,5,10,10-tetraoxide (TTO) as the acceptor unit, benzo[1,2-b:4,5-b']dithiophene derivative (Py1) and thiophene (Py2) as the donor units, respectively. The Py1/Py2 composite was prepared by physical ball milling of the two polymers in a mixture, which was further treated with a N-methyl-2-pyrrolidone (NMP)-assisted sonication treatment, and the obtained catalyst was named N-Py1/Py2. Compared with the single polymer or Py1/Py2, the FTIR characteristic peaks of O=S=O have a red shift for N-Py1/Py2, accompanied by a profound change in morphology. Furthermore, N-Py1/Py2 has a broader light response and more efficient separation and transport of charge carriers, and as a result it exhibits a higher photocatalytic hydrogen evolution rate (26.5 mmol g-1 h-1) without the involvement of any co-catalyst than Py1/Py2 catalyst (3.56 mmol g-1 h-1). The underlying mechanism for the enhanced photocatalytic activity by the sonication treatment in NMP is discussed based both on experimental and theoretical calculation data.

Pt Nanoparticles Confined in a 3D Porous FeNC Matrix as Efficient Catalysts for Rechargeable Li-CO2/O2 Batteries.

The cathodic product Li2CO3, due to its high decomposition potential, has hindered the practical application of rechargeable Li-CO2/O2 batteries. To overcome this bottleneck, a Pt/FeNC cathodic catalyst is fabricated by dispersing Pt nanoparticles (NPs) with a uniform size of 2.4 nm and 8.3 wt % loading amount into a porous microcube FeNC support for high-performance rechargeable Li-CO2/O2 batteries. The FeNC matrix is composed of numerous two-dimensional (2D) carbon nanosheets, which is derived from an Fe-doping zinc metal-organic framework (Zn-MOF). Importantly, using Pt/FeNC as the cathodic catalyst, the Li-CO2/O2 (VCO2/VO2 = 4:1) battery displays the lowest overpotential of 0.54 V and a long-term stability of 142 cycles, which is superior to batteries with FeNC (1.67 V, 47 cycles) and NC (1.87 V, 23 cycles) catalysts. The FeNC matrix and Pt NPs can exert a synergetic effect to decrease the decomposition potential of Li2CO3 and thus enhance the battery performance. In situ Fourier transform infrared (FTIR) spectroscopy further confirms that Li2CO3 can be completely decomposed under a low potential of 3.3 V using the Pt/FeNC catalyst. Impressively, Li2CO3 exhibits a film structure on the surface of the Pt/FeNC catalysts by scanning electron microscopy (SEM), and its size can be limited by the confined space between the carbon sheets in Pt/FeNC, which enlarges the better contacting interface. In addition, density functional theory (DFT) calculations reveal that the Pt and FeNC catalysts show a higher adsorption energy for Li2CO3 and Li2CO4 intermediates compared to the NC catalyst, and the possible discharge pathways are deeply investigated. The synergetic effect between the FeNC support and Pt active sites makes the Li-CO2/O2 battery achieve optimal performance.

Large-fused-ring-based D-A type electrochromic polymer with magenta/yellowish green/cyan three-color transitions.

Large-fused-ring-based conjugated polymers possess wide application prospects in optoelectronic devices due to their high charge transport and wide optical absorption. In this paper, three low-bandgap donor-acceptor (D-A) type polymers PBIT-X (X = 1, 2, 3) based on alkylated benzodithiophene and tris(thienothiophene) as donors and thiadiazol-quinoxaline as an acceptor were synthesized via Stille coupling polymerization at different (donor/acceptor) D/A molar feed ratios. The band gaps of PBIT-1, PBIT-2, PBIT-3 were 1.10 eV, 1.04 eV and 1.02 eV, respectively. Spectroelectrochemistry studies showed that the three D-A type polymers have dual bands located in visible and near-infrared regions in the neutral state. The three D-A type polymers possess good electrochromic properties, such as an optical contrast of 56% and response time of 0.3 s. In particular, PBIT-3 could achieve three color changes from magenta to yellowish green to cyan during the oxidation process. The results indicate that these D-A type conjugated polymers based on large fused-ring units exhibit multiple color changes, endowing them with huge potential applications in visible and near-infrared electrochromic devices.

Dynamic morphological transformations in soft architected materials via buckling instability encoded heterogeneous magnetization.

The geometric reconfigurations in three-dimensional morphable structures have a wide range of applications in flexible electronic devices and smart systems with unusual mechanical, acoustic, and thermal properties. However, achieving the highly controllable anisotropic transformation and dynamic regulation of architected materials crossing different scales remains challenging. Herein, we develop a magnetic regulation approach that provides an enabling technology to achieve the controllable transformation of morphable structures and unveil their dynamic modulation mechanism as well as potential applications. With buckling instability encoded heterogeneous magnetization profiles inside soft architected materials, spatially and temporally programmed magnetic inputs drive the formation of a variety of anisotropic morphological transformations and dynamic geometric reconfiguration. The introduction of magnetic stimulation could help to predetermine the buckling states of soft architected materials, and enable the formation of definite and controllable buckling states without prolonged magnetic stimulation input. The dynamic modulations can be exploited to build systems with switchable fluidic properties and are demonstrated to achieve capabilities of fluidic manipulation, selective particle trapping, sensitivity-enhanced biomedical analysis, and soft robotics. The work provides new insights to harness the programmable and dynamic morphological transformation of soft architected materials and promises benefits in microfluidics, programmable metamaterials, and biomedical applications.

Template-Free Synthesis of g-C3N4 Nanoball/BiOCl Nanotube Heterojunction with Enhanced Photocatalytic Activity.

There are many reports on g-C3N4 nanosheet and BiOCl nanosheet, but few studies on other morphologies of g-C3N4 and BiOCl. Herein, a g-C3N4 nanoball/BiOCl nanotube heterojunction prepared by a simple one-step acetonitrile solvothermal method is reported. The XRD results prove that the g-C3N4/BiOCl composites can be prepared in one step. SEM results revealed that the g-C3N4 was spherical and the BiOCl was tubular. The HRTEM results indicate that g-C3N4 has an amorphous structure and that the (100) crystal plane of BiOCl borders the g-C3N4. Spherical g-C3N4 has a narrow band gap (approximately 1.94 eV), and the band gap of g-C3N4/BiOCl after modification was also narrow. When the BiOCl accounted for 30% of the g-C3N4/BiOCl by mass, the quasi-primary reaction rate constant of RhB degradation was 45 times that of g-C3N4. This successful preparation method for optimizing g-C3N4 involving simple one-step template-free synthesis may be adopted for the preparation of diverse-shapes and high-performance nanomaterials in the future.

Anchoring NiO Nanosheet on the Surface of CNT to Enhance the Performance of a Li-O2 Battery.

Li2O2, as the cathodic discharge product of aprotic Li-O2 batteries, is difficult to electrochemically decompose. Transition-metal oxides (TMOs) have been proven to play a critical role in promoting the formation and decomposition of Li2O2. Herein, a NiO/CNT catalyst was prepared by anchoring a NiO nanosheet on the surface of CNT. When using the NiO/CNT as a cathode catalyst, the Li-O2 battery had a lower overpotential of 1.2 V and could operate 81 cycles with a limited specific capacity of 1000 mA h g-1 at a current density of 100 mA g-1. In comparison, with CNT as a cathodic catalyst, the battery could achieve an overpotential of 1.64 V and a cycling stability of 66 cycles. The introduction of NiO effectively accelerated the generation and decomposition rate of Li2O2, further improving the battery performance. SEM and XRD characterizations confirmed that a Li2O2 film formed during the discharge process and could be fully electrochemical decomposed in the charge process. The internal network and nanoporous structure of the NiO/CNT catalyst could provide more oxygen diffusion channels and accelerate the decomposition rate of Li2O2. These merits led to the Li-O2 battery's better performance.

Effect of Nitrogen Atom Introduction on the Photocatalytic Hydrogen Evolution Activity of Covalent Triazine Frameworks: Experimental and Theoretical Study.

The construction of high-performance photocatalyst has always been explored. Covalent organic frameworks (COFs), especially keto-amine-linked COFs, have many advantages, such as adjustable bandgaps, π-π stacking structure, excellent response ability to visible light, high specific surface area, high mobility of carrier carriers, good physical and chemical stability, and so on, showing strong potential applications in photocatalytic solar energy conversion and hydrogen production. Two analogous covalent triazine frameworks (CTFs), T3H-CTF and T3N-CTF, have been synthesized via Schiff-base condensation reactions between 2,4,6-trihydroxybenzene-1,3,5-tricarbalehyde (MOP) and the corresponding triazine-based aromatic amines under solvothermal condition. For T3N-CTF, the peripheral aromatic linker to the central triazine unit was the pyridine unit, instead of the benzene unit in the T3H-CTF unit. T3N-CTF had a hydrogen production rate (HPR) of 6485.05 µmol g-1 h-1 , much higher than that of T3H-CTF (2028.06 µmol g-1 h-1 ). Accordingly, T3N-CTF had a much higher apparent quantum yield (AQY) of 12.2 % than that of T3H-CTF (4.12 %) at 405 nm. The experimental and theoretical results showed that the extended light absorption range, enlarged surface area, and enhanced separation and transportation efficiencies of charge carriers of T3N-CTF compared with T3H-CTF were uniformly induced by the introduction of peripheral nitrogen atoms into the skeleton of former CTF, which eventually boosted the visible-light induced hydrogen evolution reaction (HER). The work suggests a new method for enhancing the intrinsic HER activity by modulating the electronic features of the conjugated COFs by the introduction of pyridinic N atoms.

Triazine-Based Conjugated Microporous Polymers With Different Linkage Units for Visible Light-Driven Hydrogen Evolution.

Conjugated microporous polymers (CMPs), as a kind of two-dimensional material, have attracted extensive attention due to their advantages in visible light-driven photocatalytic splitting of water for hydrogen evolution. However, improving the microstructure and electronic structure of the material to enhance their photocatalytic performance for hydrogen evolution remains a challenge. We designed and reported two analogous CMPs including CMP-1 and CMP-2 that contain triazine and dibenzothiophene-S,S-dioxide units, which were prepared by Pd-catalyzed Suzuki-Miyaura coupling reaction. The main difference of two CMPs is that the triazine units are connected to benzene unit (CMP-1) or thiophene unit (CMP-2). Both of the CMPs exhibit excellent light capture capability, and compared with CMP-2, CMP-1 has faster separation rates and lower recombination rates for the charge carriers (electron/hole), and then, a higher hydrogen evolution rate was obtained from water decomposition reaction. We find the H2 production rate of CMP-1 can be up to 9,698.53 µmol g-1h -1, which is about twice of that of CMP-2. This work suggests that molecular design is a potent method to optimize the photocatalytic performance toward hydrogen evolution of the CMPs.

Smart Adhesives via Magnetic Actuation.

Smart adhesives possess a wide range of applications owing to their reversibly and repeatedly switchable adhesion in transfer technology. Despite recent advances, it still remains a technical and scientific challenge to achieve strategies for rapidly tunable adhesion in a noncontact manner. In this study, a smart adhesive to achieve dynamically tunable adhesion is developed. Specifically, a mushroom-shaped adhesive with a magnetized tip is actuated to reversibly and rapidly transform the morphology via magnetic actuation. The smart adhesive has two working modes, namely, selective pickup mode and pick-and-place mode. In the selective pickup mode, the external magnetic field is applied and the tip undergoes bending deformation. Changes in tip morphology allow for a reversible switch of the adhesion between "turn on" and "turn off." In the pick-and-place mode, the external magnetic field is applied when the target object needs to be released. Upward bending deformation of the micro-beam, a part of the tip, creates an initial crack at the edge of the adhesion interface. The propagation of the edge crack modulates the adhesion from strong to weak and the target object is instantly released. The proposed smart adhesive may be of interest for practical applications demanding highly precise and swiftly controlled movements.

N, P, O co-doped carbon filling into carbon nitride microtubes to promote photocatalytic hydrogen production.

Carbon nitride (CN) as the photocatalytic hydrogen production catalyst has attracted great attentions but suffering from a poor performance due to the unsatisfied energy band gap and the low separation efficiency of photogenerated carriers. Herein, we create a simple method to construct a novel CN-based photocatalyst, i.e., the N, P, O co-doped carbon filled CN microtube, which presents a narrow band gap, a high separation efficiency of photogenerated carriers, and a good stability. In this novel structure, the tubular morphology of CN ensures a narrow band gap, and the N, P, O co-doped carbon facilitates the transfer of photogenerated electrons. Coupling these two further reduces the energy band gap and improves the separation efficiency. For the photocatalytic hydrogen evolution under the visible light, the optimal sample presents an ultrahigh hydrogen evolution rate of 1149.71 µmol g-1 h-1 ranking at the top level, which is 112.60 times that of traditional bulk CN. In addition, it also has a high reusability and good stability after four cycle experiments. This study has provided a new viewpoint to design or develop the high-efficient photocatalysts for hydrogen production.